Process for the production of fast dye-



.butane-diol,

tane-diol, 2:4-pentane-diol, 1.:6-hexane-diol, 2:5-hexane United States Patent Ofifice 3,073,652 Patented Jan. 15, 1963 3,073,662 PRGCESS FOR THE PRODUCTION OF FAST DYE- INGS N PQLYHYDROXYLATED MATERIALS Peter Jaeger and Eugen Johann Koller, Binningen,

Jacques Wegmann, Basel, and Heinrich Zollinger, Binningen, Switzerland, assiguors to Ciba Limited, Basel, Switzerland No Drawing. Filed Aug. 25, 1958, Ser. No. 757,146 laims priority, application Switzeriand Sept. 4, 1957 7 Claims. (Cl. 854.2)

This invention relates to a process forthe production of fast dyeings on polyhydroxylated materials.

The invention is based on the observation that fast dyeings are obtained on polyhydroxylated materials, such as polyvinyl alcohol or cellulose textile materials, when these materials are dyed with dyestuffs containing at least one water-solubilizing group and at least one reactive amino group, the textile material being treated during or after the dyeing operation with a poly-epoxide or a compound convertible under the conditions of the process into such a compound, and the material impregnated With dyestulf and the poly-epoxide being subjected to a heat treatment. As acid Water-solubilizing groups may be mentioned, for example, carboxyl groups, sulfonamide groups and more especially sulfonic acid groups.

As dyestuffs to be used in the process may be mentioned: anthraquinone dyestutfs, triphenylmethane dye stuiis, oxazine dyestutis, nitro dyestuffs, perinone dyestuffs, phthalocyanine dyestufis and more especially azodyestuiis, 'ooth metal-free dyestutfs and also their metal complexes being concerned, for example copper, nickel, chromium or cobalt complexes. These dyestuffs must contain at leastone amino group capable of reacting with the epoxy compound, for example a primary or secondary aromatically or aliphatically combined amino group or an amino group attached to an acid radical, especially a sulfonic acid radical.

As poly-epoxides (i.e. compounds containing at least two epoxy groups) to be used in the process there may be mentioned especially the di-epoxides, of which the simplest representative is butadiene dioxide of the for- I mula:

ornoHcH-om Further suitable di-epoxides' are constituted by the diglycidyl ethers of the formula:

our-ouornooutouom I 0 and those of the formula:

CH-OHCHs-OROCH2-CHCH2 in which R indicates an organic radical.

As examples of compounds corresponding to the above formula may be mentioned the diglycidyl ethers of ethylene glycol, propylene glycol, trimethylene glycol, 1:4- 1:3-butane-diol, 2: 3-butane-diol, 1:5-pendiol and 2-methyl-2:4wpentane-diol. Not only the already mentioned water-soluble poly-.epoxides but also water-insoluble epoxides can be used according to the present process if they are employed in the emulsified condition. As examples of Water-insoluble poly-epoxides may be mentioned the diglycidyl ethers of 1:4-dihydroxy-' benzene, 4:4'-dihydroxy-diphenyl. ether and more especially of 4:4'-dihydroxy-diphenyl-dimethyl propane. The.

diglycidyl ester of phthalic acid may also be mentioned. Instead of di-epoxides compounds can also be used that are converted under the conditions of the process into diepoxides, for example 2:3-dibromo-butane-diol-(1:4).

epoxide is simply added to the aqueous solution of the dyestuif concerned, preferably together with a base. In the process of the invention the goods to'be dyed are preferably dyed with such solutions in the cold or at only moderately elevated temperatures. During the dyeing process, the epoxy groups react with the amino groups of the dyestuffs and/or probably with the hydroxyl groups of the polyhydroxylated material. This reaction is accelerated by the presence ofthe above-mentioned =bases or alkali salts of weak acids. Anadvantageous embodiment of the present process consists in that the goods to be dyed are dyed on .the foulard and squeezed oil: in the usual way, advantageously so that the impregnated goods retain 0.5 to 1.3 times their original weight of dyestufi solution. When the di-epoxide is not contained in the dye bath, the dyed goods, if desired after intermediate drying, must be subsequently impregnated with an aqueous solution or emulsion of the di-epoxide. This liquor can likewise contain a base, advantageously, if no base was present in the dye bath, or it can be'diluted with a suitable organic liquid.

The fixing of the dyestuffs on the goods impregnated in this manner with dyestuffs and di-epoxide, takes place, if desired after previous drying, by heating thereof to temperatures above C., advantageously to about 140 C. In this heat treatment there is obviously produced a stable chemical combination between the dyestutf, the di-epoxide and the fiber. The resulting dyeings are therefore of excellent fastness to washing.

In some cases it may be of advantage to subject dyeings obtainable according to the present process to an after-treatment. Thus the resulting dyeings are advantageously soaped; by this after-treatment any dyestuif not completely fixed is removed.

The following examples illustrate the invention, the parts and percentages being by weight:

Example 1 A piece of cotton fabric was saturated at room ternperature in an aqueous solution containing in 100 parts 4.3 parts of the dyestufi obtained by alkaline coupling of Example 2 A cotton fabric was impregnated with a dilute aqueous solution of an alkali metal hydroxide or carbonate and the azo dyestufi described in Example 1 and dried. It was then treated at ordinary temperature in a second bath containing an aqueous'butadiene dioxide solution and left to reactfor 10 minutes'in an air bath at C. The

majority of the dyesthff thereby became fixed on the fiber fast to soa'ping' and boiling.

Example 3 Example 2 was repeated without addinga catalyst in the form of the alkali metal compound specified. By this The goods were squeezed ofi and after drying at i treatment also a dyeing was produced which after soaping was fast to washing.

Example 4 Instead of the dyestuff used in Example 1, the following dyestuffs were employed, all of which could be ixed on the fiber fast to washing and boiling with the aid of butadiene dioxide:

(a) Yellow azo dyestufi from diazotized 2-aminonaphthalene-4: 8-disulfonic acid m-toluidine.

(b) Red-brown azo dyestuit from diazotized aniline disulfonic acid- 2-hydroxy-3-naphthoic acid-(p-aminoanilide).

() Black disazo-dyestufi of the constitution HzN OH prepared by acid coupling of diazotized p-nitraniline with 1-amino-8-hydroxynaphthalene-3 6-disulfonic acid, then by alkaline coupling with diazotized aniline and reduction of the nitro group.

(d) Blue dyestuff of the formula:

in which Pc indicates a copper phthalocyanine residue,

obtainable by reaction of copper phthalocyanine- 3 :3 3 ":3 '-tetrasulfochloride with 4-aminoformylanilide or 4-aminoacetanilide and subsequent alkaline hydrolysis. V (e) Blue dyestuff of the formula in which x+y=4 and Po has the same meaning as above, prepared by the action of ammonia on copper phthalocyanine tetrasulfochloride in aqueous solution. (1) Blue dyestufi of the formula a h G -(SO2NHCH3CHz-NH2)1 in which Pc has the meaning given above.

(g) Blue dyestuif of the formula II o ism-Grin,

(in) Orange-red dyestutf containing 2mols of the monoazo dyestufi obtained by coupling diazotized l-hydroxy- 2-aminobenzene4-sulfonamide with l-(p-chlorophenyr -3-methyl'pyrazolone-5, in complex combination with 1 atom of chromium.

4 Example 6 4 parts of 2:2-di-(p-hydroxy-pheny1)-propane diglycide ether are emulsified in 20 parts of Water with the aid of a suitable emulsifier and treated with 0.5 part of a dyestufi obtained by reaction of copper phthalocyanine tetrasulfochloride with aqueous ammonia, and also 3 parts of concentrated sodium hydroxide solution. A cellulose fabric was treated with this emulsion and dried and hardened for 15 minutes at C. The dyestufi was fixed on the fiber by this treatment.

Example 7 2 parts of 2:3-dibromobutane-diol-(1:4) and 0.3 part of the azo dyestuff described in Example 1 are dissolved in 8 parts of water and treated with 2.5 parts of concentrated sodium hydroxide solution. A piece of cotton fabric was saturated with this preparation and heated for 15 minutes at C. By this treatment the dyestuft was fixed on the fiber to a high degree fast to soap and boiling.

Example 8 5 parts of ethylene glycol diglycide ether and 0.7 part of the dyestuif described in. Example 1 are dissolved in 18 parts of water and treated with 1 part of concentrated sodium hydroxide solution. Cotton fabric was impregnated with the solution and hardened at 130 C. As a result of this treatment only a small fraction of the dyestuif could be removed from the fiber.

7 What is claimed is:

1. A process for the production of fast dyeings, which comprises dyeing cotton with a dyestufi having in its molecule one to three water-solubilizing groups and an acylatable NH group, treating the cotton prior to the fixation of the dyestuff on the fiber with a compound having in its molecule a member selected from the group consisting of di-epoxy and bis-(di-hydroxy) convertible to diepoxy, groups, and subjecting the cotton impregnated with the dye-stuff and the epoxy compound to a heat treatment between 100 and C.

2. A process for the production of fast dyeings, which comprises dyeing cotton in a dye bath having in solution therein a dyestuff having in its molecule one to three water-solubilizing groups and an acylatable NH group and a compound having in its molecule two epoxy groups, prior to the fixation of the dyestufi on the fiber, and subjecting the cotton impregnated with the dyestuflf and the epoxy compound to a heat treatment between 100 and 180 C.

3. A process for the production of fast dyeings on cotton which comprises impregnating cotton with an aqueous dyeing liquor having in solution therein a dyestufiz having in its molecule one to three sulfonic acid groups and an acylatable NHg group, and butane diepoxide, prior to the fixation of the dyestufl. on the fiber, and subjecting the impregnated cotton to a heat treatment at 100-480 C.

4. A process for the production of fast dyeings on cotton which comprises impregnating cotton with an aqueous dyeing liquor having in solution therein a dyestuff having in its molecule one to three water-solubilizing groups and an acylatable NH group, butane di-epoxide, and an alkaline reacting compound, prior to the fixation of the dyestufi on the fiber, and subjecting the impregnated cotton to a heat treatment at 120-160 C.

5. A process for the production of fast dyeings on cotton which comprises impregnating cotton with an aqueous dyeing liquid having in solution therein a phthalocyanine dyestuff having in its molecule two to three sulaqueous dyeing liquor having in solution therein a phthalocyanine dyestuif of the formula wherein Fe is copper phthalocyaninyl, butadiene dioxide, and an alkali hydroxide, prior to the fixation of the dyestuff on the fiber, and subjecting the impregnated material to a heat treatment at 120-160 C.

7. A process for the production of fast dyeings on cotton which comprises impregnating cotton with an aqueous dyeing liquor having in solution therein a dyestuif having in its molecule one to three water-solubilizing groups and an acylatable NH group and then with an aqueous solution of butadiene dioxide and an alkaline reacting compound, prior to the fixation of the dyestufi on the fiber, and subjecting the impregnated cotton to a heat treatment at 120-160" C.

References Cited in the file of this patent UNITED STATES PATENTS Weinand Nov. 20, Schirm Aug. 12, Musser Nov. 30, Mackinney Nov. 15, Suen Jan. 10, Pedersen Apr. 10, Guthrie Apr. 10, Condo et al June 26, Lacey Sept. 4, Schroeder et al. Dec. 18, Enders et al. Mar. 12, Schroeder Apr. 1, Coe Jan. 20, Riat Sept. 8, Riat Sept. 29, 

1. A PROCESS FOR THE PRODUCTION OF FAST DYEINGS, WHICH COMPRISES DYEING COTTON WITH A DYESTUFF HAVING IN ITS MOLECULE ONE TO THREE WATER-SOLUBILIZING GROUPS AND AN ACYLATABLE NH2 GROUP, TREATING THE COTTON PRIOR TO THE FIXATION OF THE DYESTUFF ON THE FIBER WITH A COMPOUND HAVING IN ITS MOLECULE A MEMBER SELECTED FROM THE GROUP CONSISTING OF DI-EPOXY AND BIS-(DI-HYDROXY) CONVERTIBLE TO DIEPOXY, GROUPS, AND SUBJECTING THE COTTON IMPREGNATED WITH THE DYESTUFF AND THE EPOXY COMPOUND TO A HEAT TREATMENT BETWEEN 100 AND 180* C. 